If you are fitting a second hard drive have a look at the manufactures site, they have free tools for this purpose. I have used the Western Digital one, Data Lifeguard, a couple of times. It works well formats the drive converts to Fat32, ntfs etc and then copies the contents over to the other drive. click here
I have Win 98SE and use XXCOPY to copy everything on my C:\ drive to the D:\ drive as a complete backup, including all system files, Registry, all programs and data files. You simply go to Start/ Programs/ MS-DOS Prompt and type:-
XXCOPY C:\ D:\/CLONE
Confirming what our friend PJ123 says, you will need XXCOPY for all systems except Win XP, which will need XXCLONE.
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